Dye composition and method of use thereof for coloring thermoplastic articles

ABSTRACT

A waterless dye composition for apparel and other articles, made from thermoplastic materials, comprises an aliphatic polyester of a higher alkanoic acid and a polyol, of the formula (ACOO) 2-6  B, wherein A is alkyl of 8-22 carbon atoms and B is the residue of a polyhydric alcohol, other than glycerol, of 2-6 hydroxyl groups and an organic colorant. The compositions can further comprise an aromatic polyester of the formula C 6  H z&#39;  --(COOR 1 ) z , wherein z is 3, 4, 5, or 6; z&#39; is 6-z; and R 1  is higher alkyl; and/or a cycloaliphatic diester of the formula ##STR1## wherein R is substituted or unsubstituted straight or branched chain alkyl of 4-20 carbon atoms, polyoxyalkylene of the formula HO(C x  H y  O) n  C x  H y  -- or phosphated polyoxyalkylene of the formula (HO) 2  P(═O)O(C x  H 2x  O) n  C x  H 2x  or a salt thereof, wherein (C x  H 2x  O) n  is (CH 2  CH 2  O) n , (C 3  H 6  O) n  or (CH 2  CH 2  O) p  (C 3  H 6  O) q , n is 2-22, and the sum of p+q is n. 
     A process for coloring apparel or other articles, fabricated from polyester, polyamide, polyurethane, acrylic, halogenated polyolefin or epoxy plastic, comprises exposing an article to the foregoing compositions, maintained at a temperature between 100° C. and the temperature at which the plastic is degraded, for a time adequate to achieve the desired degree of coloration. 
     The compositions may further be diluted with water and used for textile finishing processes or as dyeing assistants in aqueous baths.

DESCRIPTION Reference to Related Applications

This application is a continuation-in-part of Wilson, Ser. No.06/702,316, filed Feb. 15, 1985, which is a continuation-in-part ofWilson, application Ser. No. 06/584,144, filed Feb. 27, 1984, nowabandoned.

TECHNICAL FIELD

This invention relates to waterless compositions, particularly adaptedfor immersion coloring of plastic articles, whether intended for apparelor general utility applications. The invention further relates to theuse of the compositions as additives for water-based systems, useful indyeing, spin finishing, or lubricating textile fibers and fabrics.

BACKGROUND ART

A continuous process for waterless dyeing of textile and plasticmaterials has been proposed by Hermes in U.S. Pat. Nos. 4,047,889 and4,055,971. The vehicle disclosed is a high boiling glycol or glycolether.

The use of ethoxylated materials for coloring of objects has beendisclosed by Lenz et al. (U.S. Pat. No. 3,362,779) and Kressner et al.(U.S. Pat. No. 4,332,587).

Hinton, Jr. et al., in U.S. Pat. No. 3,824,125, have proposed the use ofhigher trialkyl trimellitates in laundry compositions to improve soilrelease properties of synthetic fibers, such as polyesters.

Compositions containing esterified derivatives of a hydrogenatedDiels-Alder adduct of linoleic acid and acrylic acid, intended for usein various textile-treating compositions, have been disclosed by Wilson,in U.S. Pat. Nos. 4,293,305 and 4,394,126, incorporated herein byreference.

Although a variety of solvent systems have been suggested for dyeing ofarticles in waterless systems, none presently available provides rapid,failure-free dyeings, which are done without producing obnoxiouseffluents or otherwise being unacceptable from a commercial viewpoint.

It is an object of this invention to provide a composition for waterlessimmersion coloring of plastic articles, produced by the apparel andother industries. Such articles include, but are not limited to buttons,zippers, garments, carpeting, ribbons, draperies, shoe strings, sewingthread, lace, socks, plastic tubing and pipe, plastic coated wire,ropes, polyester, and polyamide films, toys, and housings for pencils,pens, kitchen utensils and telephones.

It is a further object of this invention to provide a method for rapidwaterless coloring of such articles.

DISCLOSURE OF THE INVENTION

In one aspect, this invention relates to a vehicle for waterless dipdyeing of thermoplastic articles, comprising an aliphatic polyester of ahigher alkanoic acid and a polyol, of the formula (ACOO)₂₋₆ B, wherein Ais alkyl of 8-22 carbon atoms and B is the residue of a polyhydricalcohol, other than glycerol, of 2-6 hydroxyl groups. The compositionsalso comprise glyceryl esters of acids having 9, 11, 13, 15, 17, 19 or21 carbon atoms. The compositions can further comprise an aromaticpolyester of the formula C₆ H_(z') (COOR₁)_(z), wherein z is 3, 4, 5 or6; z' is 6-z; and R₁ is substituted or unsubstituted higher alkyl or analkylphenol ether of an alkoxyalkanol and/or a diester of a hydrogenatedDiels-Alder adduct of linoleic and acrylic acids. When used as a dyebath for the coloring of thermoplastic articles, the vehicle will alsocontain sufficient amounts of an organic colorant to permit coloring ofthe thermoplastic articles being dyed.

In another aspect, this invention relates to a process for waterlesscoloring of articles, fabricated from a thermoplastic composition,comprising exposing in article to the foregoing compositions, maintainedat a temperature between 100° C. and the temperature at which theplastic degrades, for a time adequate to achieve the desired degree ofcoloration.

This invention further relates to compositions, containing one of theforegoing aromatic polyesters and one or more emulsifiers, for use inaqueous media for spin finishing, lubricating, or dyeing textileproducts, made from synthetic polymers.

"Aliphatic polyester," as used in the specification and claims, means anester of the formula (ACOO)_(v) B_(w), wherein A is alkyl of 8-22 carbonatoms and B is the residue of a polyhydric alcohol, other than glycerol,of 2-6 hydroxyl groups. The higher alkanoic acid can be selected fromacids of even or odd numbers of carbon atoms, including substituted,unsubstituted, saturated, unsaturated, branched and linear acids.Representative of acids within this class are pelargonic, decanoic,undecanoic, palmitic, myristic, oleic, stearic, linolenic and linoleicacids. The acids may be pure compounds or may be mixture of compounds,e.g., acids derived by hydrolyzing naturally-occurring fats and oils,including palm oil, corn oil, lard and the like. The aliphaticpolyesters can be made in the same fashion as the aromatic polyesters,described below.

Polyols of 2-6 hydroxyl groups include, but are not limited to ethyleneglycol, diethylene glycol, triethylene glycol, tetraethylene glycol,propylene glycol, butylene glycol, dipropylene glycol, tripropyleneglycol, trimethylolpropane, triethylolpropane, erythritol,pentaerythritol, mannitol, dulcitol, sorbitol and other isomerichexanehexols. It will be understood that the hydroxyl functions of thepolyols are completely esterified.

Preferred aliphatic polyesters are those derived from pentaerythritol,particularly pentaerythritol esters of acids having 9-21 carbon atoms,more particularly those of 9-13 carbon atoms. Pentaerythritoltetrapelargonate, trimethylolpropane tripelargonate andtriethyleneglycol dipelargonate are most preferred.

"Aromatic polyester," as used in the specification and claims, means anester formed by reaction between a polybasic aromatic acid of thebenzene series and a higher alkanol, so as to accomplish completeesterification of all carboxyl functions therein. "Higher alkanol" meansa substituted or unsubstituted alkanol of at least six carbon atoms, forexample, hexanol, octanol, 2-ethylhexanol, isodecanol, decanol,hexadecanol, octadecanol, docosanol, oleyl alcohol, linoleyl alcohol orthe like.

Also included among "higher alkanols" for the purposes of this inventionare alkylphenol ethers of alkoxyalkanols, having the formula

    C.sub.a H.sub.2a+1 --C.sub.6 H.sub.4 --O(C.sub.x H.sub.2x O).sub.b C.sub.x H.sub.2x OH,

wherein a is 1-12; b is 1-24 and x is 2 or 3, optionally includingblocks of ethyleneoxy and propyleneoxy units.

The esters can be made by reaction between, for example, trimelliticacid, and the selected alkanol, conveniently in a fashion so as toremove or entrain by-product water. Alternatively, the aromaticpolyesters can be prepared by transesterification between a lower ester,e.g. trimethyl trimellitate and the higher alkanol. In such a reaction,the lower boiling alcohol will normally be removed from the reactionsite by distillation.

Contemplated among aromatic polyesters are esters of benzene tri-,tetra-, penta- and hexacarboxylic acids, wherein R is as above.Accordingly, esters of prehnitic, mellophanic, pyromellitic, trimesic,trimellitic and hemimellitic acids are included, as well as esters ofbenzenepentacarboxylic acid and mellitic acid.

Although triesters of any of the benzenetricarboxylic acids can be used,it is preferred to use triesters of 1,2,4-benzenetricarboxylic acid,also known as trimellitic acid. Preferred esters aretris(2-ethylhexyl)trimellitate, trisisodecyl trimellitate, trisisooctyltrimellitate, tridecyl trimellitate, and trihexadecyl trimellitate. Itwill be understood that mixed esters, such as hexyl, octyl, decyltrimellitate can also be used. Most preferred istris(2-ethylhexyl)trimellitate (CAS No. 3319-31-1), also known astrioctyl trimellitate, which can be purchased from Eastman ChemicalProducts, Inc., Kingsport, Tenn., as Kodaflex® TOTM.

The compositions will preferably contain at least 5% by weight of anaromatic polyester, preferably the compounds recited above.

The aliphatic polyesters can also be admixed with a cycloaliphaticdiester of the formula ##STR2## wherein R is substituted orunsubstituted straight or branched chain alkyl of 4-20 carbon atoms,polyoxyalkylene of the formula HO(C_(x) H_(y) O)_(n) C_(x) H_(y) -- orphosphated polyoxyalkylene of the formula (HO)₂ P(═O)O(C_(x) H_(2x)O)_(n) C_(x) H_(2x) or a salt thereof, wherein (C_(x) H_(2x) O)_(n) is(CH₂ CH₂ O)_(n), (C₃ H₆ O)_(n) or (CH₂ CH₂ O)_(p) (C₃ H₆ O)_(q), n is2-22 and the sum of p+q is n. Other cycloaliphatic diester compoundswhich can be used are those wherein R is ArCOO(CH₂ CH₂ O)_(n) CH₂ CH₂--, ArCOO(C₃ H₆ O)_(n) C₃ H₆ --, ArCOO(C₂ H₄ O)_(p) (C₃ H₆ O)_(q) C₃ H₆-- or ArCOO(C₃ H₆ O)_(p) (C₂ H₄ O)_(q) C₂ H₄ --, wherein n, p and q areas above and Ar is substituted or unsubstituted mono- or bicyclic arylof up to 15 carbon atoms. The compositions of this invention can containat least 5% by weight of one or more of these cycloaliphatic diesters.It is preferred that the compositions contain a maximum of 95% by weightof the cycloaliphatic diester.

The dibasic cycloaliphatic acid employed in making the compositions ofthis invention is a Diels-Alder adduct of acrylic acid and linoleic acidand can be prepared as described by Ward in U.S. Pat. No. 3,753,968. Thediacid has the formula ##STR3## and therefore is a mixture of (5 and6)-carboxy-4-hexyl-2-cyclohexene-1-octanoic acids. The diacid isavailable commercially from Westvaco, designated as "Diacid 1550".

Preparation of adducts from conjugated octadecadienoic acid andunsaturated acids and/or their hydrogenation has also been described byTeeter et al, J. Org. Chem., vol. 22 (1957) at 512-514, Ward in U.S.Pat. No. 3,899,476 and Ward et al in U.S. Pat. No. 3,981,682.

The preparation of esters from the C₂₁ diacid adduct was reported byWard et al, J. Amer. Oil Chemists' Soc., vol. 57 (1957) at 219-224.Ethoxylated esters containing 4-119 ethylene oxide units are said to beeffective lime soap dispersants. The alkyl esters are reported as beinguseful in lubricant applications, including use as textile lubricantsand plasticizers for PVC.

The diacid can be esterified with alcohols using, for example, acidiccatalysts such as p-toluenesulfonic acid, methanesulfonic acid orsulfuric acid. During the esterification, the reaction mixture ispreferably also treated with a decolorizing agent, e.g., carbon or clay.

The diacid is reduced following esterification to a saturated compound.A nickel catalyst such as Raney Nickel, nickel on kieselguhr or nickelon alumina can be used. The required amount varies up to 5-10% by weightof the ester.

Hydrogenation is carried out after esterification to prevent nickel fromcomplexing with the free acid. Other catalysts, e.g., platinum orrhodium, avoid this problem, but are prohibitive in cost. The catalystcan be removed by filtration through a plate and frame filter press. Theproduct is the resulting filtrate.

Polyoxyalkylene diesters are prepared by reaction of the diacid, in thepresence of an alkaline catalyst, with ethylene or propylene oxide.Reaction will occur at both acid sites. Addition of ethylene oxide isallowed to continue until the product becomes at least dispersible or,preferably, soluble in water. This will correspond to addition of atotal of 5-25 ethylene oxide units. The product obtained using ethyleneoxide has a structure before hydrogenation represented by the formula:##STR4##

The phosphorylated product is readily obtained by reaction withphosphorous pentoxide. The saturated diester can be obtained bynickel-catalyzed hydrogenation.

In the case of the phosphorylated derivative, hydrogenation shouldprecede phosphorylation. The phosphorylated derivatives can be convertedto salts thereof by reaction with a metal hydroxide. Sodium andpotassium salts are preferred.

Compounds in which R is ArCOO(CH₂ CH₂ O)_(n) CH₂ CH₂ --, etc. areobtained by treating polyoxyalkylene intermediates with an aromaticacid, e.g., benzoic, toluic or mellitic acid, usually with an acidiccatalyst. Hydrogenation of the double bond in the cycloaliphatic ringcan be done before or after esterification with the aromatic acid.

Representative of substituted alkyl R which may be used in the productsof this invention are butoxybutyl, 10-hydroxystearyl, 10-hydroxydecyl,10-halostearyl, omega-alkanoyloxyalkyl or the like.

Preferred cycloaliphatic diesters for use in accordance with theprinciples of the invention are those wherein:

(a) R is straight or branched chain alkyl of 4-20 carbon atoms,

(b) R is 2-ethylhexyl, lauryl or stearyl,

(c) R is HO(CH₂ CH₂ O)_(n) CH₂ CH₂ --,

(d) R is HO(C₃ H₆ O)_(n) C₃ H₆ --,

(e) R is HO(C₂ H₄ O)_(p) (C₃ H₆ O)_(q) C₃ H₆ --,

(f) R is (HO)₂ P═O(OCH₂ CH₂)_(n) OCH₂ CH₂ -- or a salt thereof,

(g) R is C₆ H₅ CO(OC₂ H₄)_(n) OC₂ H₄ --,

(h) R is CH₃ C₆ H₄ CO(OC₂ H₄)_(n) OC₂ H₄ --

(i) R is C₆ H₅ CO(OC₃ H₆)_(n) OC₃ H₆ --, and

(j) R is CH₃ C₆ H₄ CO(OC₃ H₆)_(n) OC₃ H₆ --.

The types of plastic materials which can be colored using thecompositions and method of this invention include, but are not limitedto, polyesters, polyamides, polyurethanes, acrylics, halogenatedpolyolefins and epoxy plastics. However, textile- and apparel-relatedarticles are commonly made from polyesters, polyamides, polyurethanesand acrylics, which substrates are preferred for the practice of thisinvention. Pipe and tubing are commonly made from chlorinatedpolyethylene (CPE) or post-chlorinated PVC (PCPVC).

Polyester articles include those made from poly(alkyleneterephthalates), such as poly(ethylene terephthalate), or polyestersmade from cyclohexanedimethanol. Typical of polyester articles arepresewn garments, including slacks, jeans, dresses, shirts, scarves andthe like. Also included within the scope of polyester articles arebuttons, draperies, laces, seatbelts, ribbons, zippers and othernotions, as well as chips of polyester resins, polyester coatings onwire or metal, polyester articles (including those made from styreneatedpolyesters), polyester film, toys, components of automobiles andairplanes and housings for pencils, pens or household articles.

Polyamides particularly contemplated as substrates in the practice ofthis invention include those known as nylons 6; 6,6 or 6,10. Articleswhich can be colored in accordance with the invention include the sametypes of articles as for polyesters, as well as lingerie and hosiery. Itis common, for example, to employ polyamide teeth in zipperconstructions. Polyamides are often used for carpeting and ropes.

Acrylic plastics, contemplated within the scope of this inventioninclude straight acrylics, such as polyacrylonitrile, and modacrylics.The latter are copolymers of acrylonitrile or methacrylonitrile,generally with vinyl chloride or vinylidene chloride. Articles made fromacrylics include clothing, carpeting and notions.

Also included among acrylics are high impact resins, whether comprisingblends or graft copolymers. These are commonly identified as ABS resins.Articles made therefrom include chips, coatings for wire and metal,telephone housings, toys, impact-resistant moldings for automobiles andairplanes, and housings for pencils, pens and kitchen utensils.

Polyurethanes include a myriad of compositions, made by reaction, forexample, between glycols and organic di- or polyisocyanates. Among theglycols, used to make polyurethanes, are simple glycols, such as thealkylene glycols, and polymeric glycols, including polyether andpolyester glycols. Articles containing polyurethane, include rain wear,artificial leather, toys, and moldings and extrusions for automobilesand airplanes. Any of these articles can be colored by the teachings ofthe instant invention.

Epoxy resins include polymers in which cross-linking is brought about byan epoxy function, such as that in bisphenol A diglycidyl ether or otherglycidyl ethers. The epoxy function reacts with materials containing areactive group, for example amines, such as triethylenetetramine, andacid anhydrides, e.g. maleic anhydride and substituted maleicanhydrides. Most commercially available epoxy resins are based onbisphenol A diglycidyl ether. Epoxy resins are used in coatings and forencapsulating electrical components.

In some instances, the foregoing types of plastics can be blended withnatural or synthetic cellulosic materials and colored according to thisinvention.

"Organic colorant," as used in the specification and claims, includesboth dyes and pigments of any structure. Normally, the dyes or pigmentswhich are employed need not be soluble in water. Therefore, such dyesand pigments will not usually contain water-solubilizing functions, suchas a plurality of sulfonic acid groups. The dyes/pigments used in thepractice of this invention generally will be chosen from amongwater-insoluble dyes, which may also be known as disperse dyes. Includedwithin this class of dyes, which can be used on fibers such as celluloseacetate, polyamides or polyesters, from any kind of dyeing medium arecolors of azo, azomethine, nitroarene and anthraquinone structures. Itwill be understood that the dyes useful in the practice of the presentinvention are not limited to these classes of compounds.

The dyes or pigments used in the practice of this invention may beidentified by their chemical names, for example:

3-nitro-N⁴ -phenylsulfanilanilide, a yellow dye;p-[p-(phenylazo)phenylazo]phenol, a red-yellow dye; ethyl4-hydroxy-1-anthraquinonecarbamate (an orange dye);1-amino-4-hydroxyanthraquinone, a red dye;1-amino-2-bromo-4-hydroxyanthraquinone, a red-blue dye or4,5-diaminochrysazin, a blue dye.

The dyes alternatively may be identified in accordance with standardchemical handbooks, such as "The Color Index," third edition. TheSociety of Dyes and Colors and the American Association of TextileChemists and Colorists (1971). This sort of handbook correlates dyestructure with trade names. Typical of colorants identified inaccordance with this handbook, which can be used in the practice of thisinvention, are Solvent Orange 20; Acid Blue 83 (C.I. 42660), Acid Blue59 (C.I. 50315), Direct Blue 86 (C.I. 74180); Direct Red 81 (C.I. 28160)and Acid Yellow 36 (C.I. 13065).

Cationic dyestuffs can also be used in the practice of this invention,for example Rhodamine 6G, Rhodamine B, Rhoduline Blue 6G and MethyleneBlue BB.

Similarly, metallized azo dyestuffs can be employed in the practice ofthis invention. Representative metallized azo dyes which can be employedare Co, Ni, Cu or Cr complexes of coupling products of2-amino-4-nitrophenol and resorcinol; 2-amino-4-chloro-5-nitrophenol andacetoacetanilide; dianisidine and 3-hydroxy-2-naphthanilide;2-amino-4-chloro-5-nitrophenol and 2-aminonaphthalene or the like.

It will further be understood that other textile-treating agents, suchas optical brighteners, e.g. styrylnaphthoxazole compounds, can beapplied, along with dyes or pigments.

The dyes/pigments can be used in any form, that is, as presscake or asdried pressed dye. The addition of dispersing agents is optional.Alternatively, the dyes or pigments can be added to the dye bath in asolvent/dispersing medium compatible with the dye bath. It is convenientand preferred, in the practice of this invention, to use solid dispersedyes free of additives.

It has been found that waterless dye baths containing at least 5% byweight of an aromatic polyester can be decolorized using activatedcarbon, whereas baths of prior art compositions, containing no aromaticpolyester are not readily decolorized in this fashion. Most preferably,these compositions contain at least 5% by weight of trialkyltrimellitate, wherein alkyl is of 6-22 carbon atoms.

Addition of triphenyl phosphite to the dye baths has been found toreduce discoloration of the dye bath. Accordingly, compositionscontaining 0.1-2.0% by weight of triphenyl phosphite are preferred. Thebaths can contain, in addition to or instead of triphenyl phosphite,0.1-2.0% by weight of 2,2'-oxamido bis[ethyl3-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionate].

Optional emulsifiers or dyeing assistant agents, used in thecompositions of this invention, include, but are not limited to,alkoxylated alkylphenols and their esters, alkoxylated castor oilcompounds, alkoxylated hydrogenated castor oil compounds, alkoxylatedprimary alkanols, salts of phosphated alkoxylated primary alkanols oralkylphenols, ethoxylated sorbitan esters and mixtures thereof. Theseoptional emulsifiers or dyeing assistant agents can be used in thewaterless dyebath compositions or in lubricant, spin finishing or dyeingbath additives, for aqueous dye baths, in accordance with Wilson, U.S.Pat. Nos. 4,293,305 and 4,394,126.

The amount of optional emulsifier or dyeing assistant agent, employed inthe compositions of this invention, is at least about 0.5% by weight ofthe composition and can be as high as 60-80% by weight. Waterless dyebath compositions will preferably contain 5-10% by weight of one or moreoptional emulsifiers.

Ethoxylated alkanols, used as optional emulsifiers, will be of alkanolsof 8-24 carbon atoms, ethoxylated so as to contain 2-30 ethyleneoxyunits. Typical ethoxylated alkanols which can be used are lauryl alcohol3.5 ethoxylate (POE 3.5) or POE (18) tridecyl alcohol.

Preferred optional dyeing assistant agents are alkoxylated alkylphenolsand their esters. These are compounds of the formula

    C.sub.a H.sub.2a+1 --C.sub.6 H.sub.4 --O(C.sub.x H.sub.2x O).sub.b R",

wherein a is 1-12; b is 1-24; R" is H, aroyl of mono- or bicyclicaromatic acids of up to 15 carbon atoms or substituted or unsubstitutedalkanoyl of 8-30 carbon atoms. Accordingly, exemplary dyeing assistantagents include ethoxylated and propoxylated alkyl phenols andcorresponding esters, such as the laurate, myristate, palmitate,coconate, oleate, stearate, isostearate, benzoate and toluate esters.Preferred alkylphenols are nonylphenol, octylphenol, and dodecylphenol.

It will be understood that the alkylphenols and the acids used toesterify the alkoxylated alkylphenols can include mixtures.

Most preferably, the alkoxylated alkylphenols will be ethoxylatedderivatives, having 5-10 ethylene oxide units.

Preferred emulsifiers or optional dyeing assistant agents will be thosewherein:

(a) R" is alkanoyl of 12-18 carbon atoms, including mixtures thereof;

(b) R" is n--C₁₇ H₃₃ CO;

(c) R" is n--C₁₇ H₃₅ CO;

(d) R" is iso--C₁₇ H₃₅ CO;

(e) R" is benzoyl;

(f) R" is n--C₁₁ H₂₃ CO;

(g) R" is H;

(h) a is 5-10, including each of (a)-(g);

(i) b is 6-15, including each of (a)-(h);

(j) b is 8-11, including mixtures thereof and including each of (a)-(h);

(k) a is 9, b is 8-10 and R" is n--C₁₁ H₂₃ CO;

(l) a is 9, b is 6-10 and R" is H and

(m) x is 2, including each of (a)-(l).

Alkoxylated castor oil used as an optional additive in the compositionof this invention will contain 15-100 oxyalkylene units, preferably40-85 oxyethylene units. The hydrogenated castor oil derivatives willcontain 5-200 oxyalkylene units, preferably 20-30 oxyethylene units.These types of materials can be purchased from ICI America andWhitestone Chemical Co.

It has been found, in accordance with this invention that articles canbe dyed or colored very rapidly and very homogeneously. Normally,immersion in the dye bath for as little as 30 seconds at 160° C. willgive significant coloration. However, for even faster results, thedyeings can be done at 180°-200° C. or higher. Employing thecompositions of this invention at 200° C. or more does not result insmoking or pollution of the processing plant, which is a problem whenethylene glycol or diethylene glycol are the dyeing solvents. Inpractice, it is feasible to use a temperature, up to that at which theplastic being dyed, will degrade. However, temperatures between120°-235° C., most preferably 140°-235° C., will be preferred.

Although it is preferred to dye the articles being treated by immersionin a bath of the dye composition, the dyes can also be applied byspraying. Then, the sprayed articles should be heated in a bath to atleast 140° C. to complete uptake of the dye into the article.

Whether the article is dyed by immersion or otherwise, the dyed articleis normally cleaned with a solvent to remove excess dye. Preferably, thesolvents used for cleaning are chlorinated or fluorinated hydrocarbons.However, highly chlorinated solvents, such as perchloroethylene andtrichloroethylene are preferred for cleaning by immersion in a liquidbath. Fluorochlorocarbons, such as dichlorodifluoromethane,chlorotrifluoromethane, which are gases at ambient temperatures orslightly above, can be used for vapor-phase cleaning of the dyedarticles. Normally, means will be used to recover and recycle thecleaning solvent, rather than discharging it to the atmosphere.

A further advantage of the process of the invention is that it isessentially self-contained and effluent free, that is, little or nomaterial is lost or discharged to the atmosphere.

In the apparatus of this invention, the major components include a diptank, a dye recovery unit, a solvent cleaning tank, a solvent recoverystill and a drier. The dip tank will be provided with heating means andstirring means, so as to permit circulation of the dyeing solutionwithin the dip tank and to a dye recovery unit external thereto.

The dye recovery unit normally includes filtration means for removal ofsolid debris from used dye solutions and distilling and condensing meansfor recovery of the solvent. The purified dye solution can be recycledto the dip tank, with addition of dye or other additives to provide thedesired composition in the dip tank, or can be stored for later use.

It is preferred, in coloring many types of textile-related articles,including jeans, shorts, lingerie, carpeting, hosiery, zippers and lace,as exemplary, to provide squeeze roller means, essentially functioningas wringers, to remove excess dye solution from treated articles. Thedye solution removed at this point can be cycled to the externalrecovery unit or can be returned directly to the dip tank.

When the dye bath contains at least 5% by weight of aromatic polyesterand is free of other optional dyeing assistant agents, it is preferredto recover clean dye vehicle by treatment with activated carbon. Thetreatment permits reuse of the dyeing vehicle with a plurality ofdifferent organic colorants and avoids the need for recovering thedyeing vehicle by distillation.

Articles leaving the squeeze roll station are passed into the solventcleaning tank to complete removal of any excess or unadherent dyematter. It is preferred to use a plurality of solvent cleaning tanks. Itis also preferred to circulate solvent from the tank through an externalsolvent recovery unit, provided with filters to remove solid materialsand distilling and condensing means for purifying solvent, and to returnpurified solvent to the system. Dye recovered on the filter or asresidue from the distillation can be returned to the system for recycle.When a plurality of solvent cleaning tanks are employed, it is preferredto flow solvent countercurrently to the direction in which the articlesbeing treated, are moved.

The final component of the apparatus is the drying means, such as a hotair drier, from which articles leaving the system can be inspected andpackaged. Solvent vapors from the hot air drier can be condensed andreturned to the system.

Textile-processing compositions, other than waterless dye bath media,used in the practice of this invention, can be applied at any of severalstages of fiber processing. The following are exemplary of applicationto polyester fiber.

A. Spin Finish Application

The spin finish is applied to the yarn from a 10-20% emulsion to give afinish level on the yarn of 0.25-10%. The treated yarn can be built intoyarn packages which can be used in high speed texturizing machines.

Compositions used as spin finishes will preferably have the followingcompositional range:

    ______________________________________                                        parts by weight                                                               ______________________________________                                         1-40          aliphatic polyester                                            20-60          aromatic polyester                                             10-50          emulsifiers and optional additives                             ______________________________________                                    

Most preferably, the compositions will contain 25-35 parts by weight ofthe aliphatic polyester and 25-35 parts by weight of aromatic polyester.However, acceptable spin finish compositions are obtained using aromaticpolyester and emulsifiers and other additives as the sole components.

Spin finish compositions will preferably contain an aliphatic polyesterin which A is alkyl of 8-20 carbon atoms, most preferably 8-12 carbonatoms. The aromatic polyester will preferably be as above.

Preferred optional dyeing assistant agents will be ethoxylatednonylphenol esters, particularly in combination with one or more ofethoxylated castor oil, ethoxylated hydrogenated castor oil and/orphosphated ethoxylated alkylphenol.

A most preferred spin finish composition will consist essentially of:

    ______________________________________                                        parts by weight                                                               ______________________________________                                        25-35         pentaerythritol tetrapelargonate                                25-35         trioctyl trimellitate                                           10-20         ethoxylated nonylphenol laurate                                 4-6           ethoxylated castor oil                                           8-12         ethoxylated hydrogenated castor oil                              8-12         ethoxylated nonylphenol phosphate,                                            K salt                                                          ______________________________________                                    

The spin finish compositions can be diluted with water to form a stableemulsion or dispersion. The spin finish is preferably applied to producea pick-up of 0.4-0.75% by weight.

A representative polyester treated to a 0.5-0.6% pick-up with the spinfinish of this invention will have lower heat history characteristicsthan yarn treated with a conventional spin finish. Yarns thus treatedcan accordingly be texturized at lower temperatures than possiblepreviously and can be dyed in an aqueous bath at lower temperatures thanpreviously used. In addition, the spin finish will not smoke or fumeduring texturizing at 200°-240° C.

It is recommended that, after the spin finishing compositions of thisinvention have been applied, no further lubricants be used, so as toprevent adulteration of the finishes. Maximum benefit will be obtainedby exclusive use of the compositions of the invention through conversionof the treated yarn to piece goods and dyeing.

B. Knitting Applications

The composition is applied as a knitting lubricant and is left on theyarn during downstream yarn processing. That is, the lubricant need notbe scoured off as are conventional lubricants. The capability ofomitting a previously-required processing step is an important advantagein utilizing the teachings of this invention. During weaving orknitting, high temperatures are reached due to friction, but thelubricants of this invention will remain functional and not gum up orbuild up on the equipment.

In dyeing in an aqueous dye bath, the lubricant does not break downduring the dyeing cycle or smoke during drying and heat setting of thefiber. Elimination of hazy blue smoke during drying and heat setting isimportant because of increasingly stringent restrictions on airpollution.

The lubricant compositions of this invention will preferably be asfollows:

    ______________________________________                                        parts by weight                                                               ______________________________________                                         1-30          aromatic polyester                                             30-90          aliphatic polyester/mixture                                    10-60          emulsifiers and optional additives                             ______________________________________                                    

Most preferably, the compositions will contain 50-75 parts by weight ofaliphatic polyester, 1-15 parts by weight of aromatic triester and 15-45parts by weight of optional dyeing assistant agents. Preferredingredients are as above. Also preferred are compositions containing amixture of trimethylolpropane tripelargonate and triethyleneglycoldipelargonate. As noted above, water-based compositions, containing nocycloaliphatic diester, are entirely acceptable.

Other materials in the lubricant composition can include an antioxidant,such as butylated hydroxytoluene, in an amount up to about 0.5% byweight; an alkanolamine, such as triethanolamine, in an amount up toabout 5.0% by weight; and up to about 2.5% by weight of water.

A most preferred lubricant composition comprises:

    ______________________________________                                        parts by                                                                      weight                                                                        ______________________________________                                        60-75  trimethylolpropane tripelargonate and                                         triethyleneglycol dipelargonate                                        1-5    trioctyl trimellitate                                                  15-35  ethoxylated hydrogenated castor oil (25 EO units)                      0-5    chlorowax                                                              optional                                                                             triphenyl phosphite/2,2'-oxamidobis[ethyl 3-(3,5-di-tert.-                    butyl-4-hydroxyphenyl)propionate]                                      ______________________________________                                    

For satisfactory performance, the take-up, expressed as minimum percentextractables, when the treated fiber or fabric is loaded into the dyeingmachine, should be at least 0.075% by weight of aliphatic polyester.

C. Application as Coning Oil

Coning oil is applied after texturing or while the yarn is being wound.For this use, the compositions will also contain a major amount, up to70% by weight, of ethylene oxide-propylene oxide copolymers of 2000-5000molecular weight. Typical materials, which are appropriate, are Ucon® LBand HB (Union Carbide Co.) and the Pluronics® (BASF) or Jeffox fluids(Texaco, Inc.).

Coning oils in accordance with the invention will include:

    ______________________________________                                        parts by weight                                                               ______________________________________                                        1-10      aliphatic polyester                                                 5-20      aromatic polyester                                                  2-20      emulsifiers and optional dyeing assistant agents                    60-70     ethylene oxide-propylene oxide copolymer                            ______________________________________                                    

Preferred compositions will contain aliphatic polyesters, wherein A isof 8-20 carbon atoms, most preferably 8-12 carbon atoms and atrimellitate ester. The optional dyeing assistant agent will preferablybe an ester of an ethoxylated alkylphenol, most preferably nonylphenol.Other preferred additives will be ethoxylated alkanols, thecorresponding phosphates and ethoxylated hydrogenated castor oil.

Coning oil compositions can also include up to about 0.5% by weight ofan antioxidant, such as butylated hydroxytoluene; up to about 2.5% byweight of an alkanolamine and up to 2.5% by weight of water.

D. Dyeing

Dyeing assistant agents, for aqueous dye baths, will consist of:

    ______________________________________                                        parts by weight                                                               ______________________________________                                         1-40          aliphatic polyester                                            20-90          aromatic polyester                                             10-30          optional dyeing assistant agents                               ______________________________________                                    

The aliphatic polyesters utilized for this aspect of the invention willpreferably be those in which A is alkyl of 8-20 carbon atoms, mostpreferably of 8-12 carbon atoms. Preferred aromatic polyesters aretrimellitates, most preferably trioctyl trimellitate.

It has surprisingly been found that aqueous and non-aqueous dye bathscontaining aromatic polyester, with or without emulsifiers or otheroptional dyeing assistant additives, but no cycloaliphatic diester, havebetter high temperature stability than compositions containing both thearomatic polyester and the cycloaliphatic diester.

Preferred emulsifiers and optional additives will be esters ofethoxylated alkylphenols, most preferably ethoxylated nonylphenol.Preferred compositions will also contain at least one of ethoxylatedcastor oil or ethoxylated hydrogenated castor oil or a phosphatedderivative (K salt) of an ethoxylated cycloaliphatic diester (R isphosphated polyoxyethylene).

A most preferred dyeing assistant composition will contain:

    ______________________________________                                        parts by weight                                                               ______________________________________                                        25-35        pentaerythritol tetrapelargonate                                 35-45        trioctyl trimellitate                                            10-20        POE nonylphenol laurate                                          4-6          POE castor oil                                                    8-12        POE hydrogenated castor oil                                       8-12        POE cycloaliphatic diester phosphate,                                         K salt                                                           ______________________________________                                    

The composition is applied to the dyebath at a level of about 0.25% byweight of the goods entering the acidic (pH=5±0.5) dyebath. The onlyadditional ingredients in the bath are water and the colorant. This isunlike conventional processes, in which the dyeing assistant agent isadded in amounts of 2-4%, by weight, along with auxiliary levellingagents.

Dyed yarns obtained using the compositions of this invention comparefavorably with conventionally-dyed yarns with respect to properties suchas light-fastness, crocking, shade depth and levelness.

BEST MODE FOR CARRYING OUT THE INVENTION

In a most preferred aspect, the compositions of this invention willcontain 15-90% by weight of aromatic polyester, 90-15% by weight ofaliphatic polyester and an organic colorant, wherein the aromaticpolyester is a trialkyl trimellitate in which alkyl is of 6-20 carbonatoms, the aliphatic polyester is one wherein A is of 8-20 carbon atomsand the organic colorant is a disperse dye.

A most preferred process in accordance with this invention is onewherein the article being treated is exposed to the foregoingcomposition, maintained at a temperature of 140°-235° C. for a timeadequate to achieve the desired degree of coloration.

Without further elaboration, it is believed that one skilled in the artcan, using the preceding description, utilize the present invention tothe fullest extent. The following specific embodiments are, therefore,to be construed as merely illustrative and not limitative of theremainder of the disclosure in any way whatsoever. In the followingexamples, the temperatures are set forth uncorrected in degrees Celsius.Unless otherwise indicated, all parts and percentages are by weight.

EXAMPLE 1 Preparation of Pentaethryritol Tetrapelargonate

To a 3-necked flask fitted with stirrer, condenser, receiver,thermometer, nitrogen purge and heating mantle are charged 1.1 mole ofpentaerythritol, 4 moles of pelargonic acid and 0.8 g ofp-toluenesulfonic acid. Air is purged from the flask with nitrogen andthe contents of the flask are heated to 160°-170° C. Water formed by thereaction is removed continuously. The reaction is continued until theproduct has an acid value below 5 mg KOH/g. The product is cooled andfiltered.

Other esters are prepared using the following reactants:

(1) trimethylolpropane and dodecanoic acid 1:3 molar ratio

(2) pentaerythritol and palmitic acid 1:4 molar ratio

(3) trimethylolpropane and pelargonic acid 1:3 molar ratio

(4) triethyleneglycol and pelargonic acid 1:2 molar ratio

(5) diethyleneglycol and undecanoic acid 1:2 molar ratio

(6) trimethylolethane and a mixture of stearic and oleic acids 1:3 molarratio

(7) mannitol and tetradecanoic acid 1:6 molar ratio.

EXAMPLE 2 Preparation of Polyoxyethylene Nonylphenyl Laurate

To a three-necked flask fitted out with stirrer, condenser, receiver,thermometer, nitrogen purge and heating mantle were charged 750 g (1.1moles) of polyoxyethylated nonylphenol (9.5 moles of oxyethylene, NP9.5), 208 g (1 mole) of lauric acid and 2.4 g of p-toluenesulfonic acid.Air was purged from the flask with nitrogen and the mixture was heatedto 160°-170° C. Water was removed continuously. The reaction was allowedto continue until an acid value below 10 mg/KOH was obtained for asample of product. The product was cooled and filtered.

Other polyoxyethylene compounds are made in a similar fashion from:

(1) NP 9.5 and coconut fatty acid, 1:1 molar ratio

(2) NP 9.5 and oleic acid, 1:1 molar ratio

(3) NP 9.5 and stearic acid, 1:1 molar ratio

(4) NP 9.5 and benzoic acid, 1:1 molar ratio.

EXAMPLE 3 Preparation of Cycloaliphatic Diester (R is 2-ethylhexyl)

To a three-necked flask fitted with stirrer, thermometer, nitrogenpurge, condenser, side-arm receiver and heating mantle were charged 352g (1 mole) of Diacid 1550, 273 g (2.1 moles) of 2-ethylhexanol, 1.5 g ofp-toluenesulfonic acid and 2 g of decolorizing carbon. Air was purgedfrom the flask with nitrogen and the reaction mixtue was stirred andheated to 160°-170° C. for 4-6 hours. Water formed during the reactionwas collected in the side-arm receiver. The reaction was continued untilthe acid value was below 5 mg KOH/g. The catalyst and carbon wereremoved by filtration. The ester product and 25 grams of nickel onkieselguhr were charged to a stirred, heated pressure vessel. Themixture was heated to 160°-170° C. and pressurized to 400 psig withhydrogen. A sample was removed after 6-8 hours for determination of theiodine value. The reaction was continued until the iodine value wasbelow 0.5 g of iodine/100 g of sample.

The product was cooled to 50° C. and the catalyst was removed byfiltration.

Esters are prepared similarly from:

(1) Diacid 1550 and decyl alcohol, 1:2 molar ratio

(2) Diacid 1550 and tridecyl alcohol, 1:2 molar ratio

(3) Diacid 1550 and Neodol 25 (a mixture of 12-15 carbon alcohols), 1:2molar ratio.

EXAMPLE 4 A. Preparation of Polyoxyethylene Unsaturated CycloaliphaticDiester, R is HO(CH₂ CH₂ O)_(n) CH₂ CH₂ --)

To a stirred autoclave fitted with heating and cooling coils was charged352 g (1 mole) of Diacid 1550. Catalyst (1.0 g of potassium hydroxide)was charged to the reactor. The temperature was raised to 110° C. andthe reactor was vacuum stripped for 30-60 minutes to remove any residualwater from previous washing of the reactor or from one or more of thecharged reactants or catalyst. The reactor was purged with nitrogen toremove air, evacuated again and purged again with nitrogen. The contentsof the reactor were stirred and heated to 140° C. and 100 g (2.3 moles)of ethylene oxide was added to the reactor. The pressure inside thereactor immediately built up to 30-50 psig. After 30-60 minutes'induction time, an exothermic polymerization reaction (to 150°-160° C.)began. The reaction was accompanied by a pressure drop to zero (0 psig)as the ethylene oxide was consumed. Ethylene oxide was added to thereactor to a total of 660 g (15 moles). The temperature was maintainedat 150°-160° C. by cooling. Addition of ethylene oxide was stopped andthe reaction was allowed to continue for 30 minutes more. The reactorwas cooled to 90°-100° C. and purged twice with nitrogen.

A sample of the product had a hydroxyl value of 110 mg of KOH/g (15moles of ethylene oxide added to the diacid). The diester was acidifiedwith acetic acid to neutralize the potassium hydroxide catalyst andtreated with 3 g of hydrogen peroxide to bleach and lighten the color ofthe product. The reactor was cooled to 30° C. prior to removing theproduct, which was filtered through filter paper, using a porcelainfilter.

B. Reduction to the Polyoxyethylene Diester

The product of Example 4A and 25 g of nickel on kieselguhr were chargedto a stirred, heated pressure vessel. The mixture was heated to160°-170° C. and pressurized with hydrogen to 400 psig. After 6-8 hours,samples were removed at intervals for determination of the iodine value.The reaction was continued until the iodine value was less than 0.5g/100 g of sample.

EXAMPLE 5 Preparation of Phosphated Polyoxyethylene Diester (R is (HO)₂P(═O)(OCH₂ CH₂)_(n) --OCH₂ CH₂ --)

Polyoxyethylated (15 moles of ethylene oxide) diacid, obtained as inExample 4B was heated to 50°-60° C., stirred and purged thoroughly withnitrogen to remove air. To about 1015 g (1 mole) of this material wasadded 24 g (0.17 mole) of phosphorus pentoxide. An exothermic reactionbegan immediately, with an exotherm to 85°-95° C. The reaction mixturewas maintained at this temperature by cooling and an additional 24 g(0.17 mole) of phosphorus pentoxide was added. The reaction wascontinued for three hours after all of the phosphorus pentoxide wasadded. The reactor was cooled to 50° C. prior to removal of a sample.The acid value of the product was 32 mg KOH/g, indicating that thereaction was complete. The batch was bleached at 85°-95° C. with 5 g ofhydrogen peroxide, cooled to 30° C. and filtered.

EXAMPLE 6 Aroylpolyoxyethylene Cycloaliphatic Diester

An aroylpolyoxyethylene cycloaliphatic diester was synthesized in atwo-liter autoclave fitted with nitrogen purge, condenser and receiverfor the removal of by-product water. Charge weights were:

510.0 g. Diacid 1550

2.0 g. flake caustic

636.0 g. ethylene oxide

After purging the system with nitrogen, Diacid 1550 and caustic wereheated to 130° C. Ethylene oxide was added over a four-hour period,during which the temperature was kept at 150°-165° C. The resultingethoxylated product was cooled to 90° C. for removal of a sample. Thehydroxyl value was 139. To this intermediate was added:

3.5 g. acetic acid (glacial)

7.5 g. methanesulfonic acid (70%)

340.0 g. benzoic acid

After purging with nitrogen, the temperature of the mixture was raisedto and held at 165°-170° C. until the acid value was less than 5 mg KOHper gram. The theoretical amount of water was removed during thereaction and collected in the receiver. The sample was cooled andfiltered.

The filtered product was hydrogenated in a two-liter autoclave:

1000.0 g ethoxylated product, above

50.0 g Raney nickel

QS hydrogen

The reduction was run at 100°-125° C. and 200-250 psig until hydrogenconsumption ceased. The product was cooled and filtered.

EXAMPLE 7

Ethoxylated castor and hydrogenated castor oils were prepared as inExample 4. Ethylene oxide adds to the hydroxyl group of castor oil.

EXAMPLE 8

A waterless dyeing composition was prepared frombis(2-ethylhexyl)cycloaliphatic diester of Example 3 andtris(2-ethylhexyl)trimellitate (Eastman) in 20:80 weight ratio,containing 5 grams/liter of Disperse Blue 60 and 0.1% by weight oftriphenylphosphite.

This composition was kept at 185° C. and stirred while a piece ofpolyester carpet was immersed therein for 30 sec. The carpet section wasremoved, washed in perchloroethylene and dried. The carpet washomogeneously colored with good dye fixation. There was little or nosmoking during the coloring operation.

EXAMPLE 9

Dip dye solution was made from 80 parts by weight oftris(2-ethylhexyl)trimellitate, 20 parts by weight ofbis(2-ethylhexyl)cycloaliphatic diester and 0.1% by weight of triphenylphosphite.

To this was added Sandoz Pigment Yellow 2B at a level of 5 g/l. Theresulting composition was used to dye a piece of nylon carpet (200° C.,2 min). The experiment was otherwise as in Example 8. The nylon carpetwas dyed yellow with good levelness.

EXAMPLE 10

Pure tris(2-ethylhexyl)trimellitate was used to dye nylon and polyestersamples with Disperse Blue 56 (5 g/l) at 185° C. for 30 sec. Resultswere similar to those of Examples 8 and 9. Similarly good results wereobtained, using 10 g or 20 g/l of the same dye.

EXAMPLE 11

A dye bath was prepared from a mixture of 50 g oftris(2-ethylhexyl)trimellitate and 50 g of pentaerythritoltetrapelargonate, to which was added 0.5 g of Disperse Blue 56 dye.

The resulting dark blue mixture was heated to 185° C. and maintained atthat temperature to dye a swatch of polyester fabric. The immersion timewas 1 min. The dyed swatch was washed with perchloroethylene and dryed.The dyed sample was a level, dark blue shade.

EXAMPLE 12

Baths were made from tris(2-ethylhexyl)trimellitate and pentaerythritoltetrapelargonate in 20:80 and 80:20 ratios by weight. The solutions,containing 0.5 g of Disperse Blue 56, were used to dye polyester fabricswatches at 185° C. as in Example 11. Slightly lighter shades of bluewere obtained.

EXAMPLE 13

(a) Dye solution comprising ethylene glycol, containing 1 gram/liter ofpure presscake blue dye, was heated to 180° C. with constant stirring.The solution began to smoke at about 107° C. Smoking became verytroublesome at 125° C. and even worse at 180° C.

Into the solution at 180° C. was immersed a six-inch piece of polyesterzipper. After one minutes' immersion, the zipper was removed, cooled inair and cleaned in perchloroethylene solution, to remove residual dyesolution. The zipper was difficult to clean. The zipper was unevenlycolored and had many splotches.

(b) A similar experiment was done, using diethylene glycol as solvent.The dyed product was unevenly dyed and had many splotches.

These experiments demonstrate that use of glycol solvents isunacceptable from a pollution standpoint and that unacceptable dyeingsare obtained.

EXAMPLE 14

A 3/16 inch stainless steel tank of 70 gallon capacity containing 520pounds of dip dye solution of glyceryl tribenzoate and nonylphenol 7(oxyethylene units, Union Carbide Corp.) in 20:80 weight ratio, at a dyelevel of 0.5 pound of Latyl Blue BCN 356 (crude ground dye) was heatedexternally to provide a temperature of 182° C.

A pump was used to circulate material in the dye bath during heating andwhile a polyester zipper about two feet long was immersed in the stirredbath for about 30 seconds. The zipper was removed from the bath andlightly squeezed with a roller to remove excess dye solution. The zipperwas washed in a tank containing a mixture of trichloroethylene andperchloroethylene. After 30 seconds' immersion in the bath, the zipperwas dried in a hot air chamber. The zipper was ready for finalinspection and shipment.

The zipper was rapidly dyed by this method and was pleasant inappearance.

EXAMPLE 15

Textile-treating compositions are made by combining materials preparedas above in the following amounts by weight:

    ______________________________________                                        parts by weight                                                               A       B                                                                     ______________________________________                                        20       1      pentaerythritol tetrapelargonate                              40      59      trioctyl trimellitate                                         20      20      polyethoxyethylene nonylphenol laurate                                        (9.5 moles ethylene oxide)                                    10      10      polyethoxyethylene hydrogenated castor                                        (25 moles ethylene oxide)                                     10      10      polyethoxyethylene castor                                                     (80 moles ethylene oxide)                                     ______________________________________                                    

EXAMPLE 16

The textile-treating compositions of Example 15 are applied during thedyeing cycle to a 10 g swatch of T56 textured polyester fabric by thefollowing technique:

A sample swatch is placed in a stainless steel beaker containing 150 mlof water, 0.067 g of disperse yellow 67, 0.091 g of disperse blue 56,0.1 g of acetic acid (56%) and 0.03 g of textile-treating composition.The beaker is sealed and placed in a launderometer set at 38° C. Thetemperature is raised at 4°-5° C./min to 130° C. and held for 30 min.The beaker is cooled at 4°-5° C./min to 52° C. and removed from thelaunderometer. The polyester swatch is removed from the beaker. It isuniformly dyed in a medium brown shade. Nearly all of the dye isexhausted from the aqueous solution.

EXAMPLE 17

Textile-treating compositions are prepared as in Example 15 from:

    ______________________________________                                        parts by weight                                                               A       B                                                                     ______________________________________                                        30.0     1.0      pentaerythritol tetrapelargonate                            30.0    59.0      trioctyl trimellitate                                       15.0    15.0      POE (9.5) nonylphenol laurate                                5.0     5.0      POE (80) castor oil                                         10.0    10.0      POE (25) hydrogenated castor oil                            10.0    10.0      POE (15) diester phosphate, K salt                                            (Example 5)                                                 ______________________________________                                    

(b) The compositions thus obtained are applied from a 20% aqueoussolution as a spin finish to 150 denier polyester fiber, which is thenspun and textured.

Spin finish, applied as above, does not smoke, drip, build up on heaterplates or cause other undesirable conditions.

The texturized yarn is knitted into a double knit fabric. The yarn knitswell. No haze, mist or odor is observed in the knitting plant.

The fabric is taken to the dyehouse and loaded into a 6-port GastonCounty jet machine. The goods are neither overflow washed nor scoured.Foaming during loading of the fabric is significantly lower than that offabrics treated with conventional lubricants. A good dyeing is obtained.

EXAMPLE 18

(a) Spin finishing compositions are prepared from:

    ______________________________________                                        parts by weight                                                               A       B                                                                     ______________________________________                                        30       1        pentaerythritol tetrapelargonate                            30      59        trioctyl trimellitate                                       15      15        POE (9) nonylphenol laurate                                  5       5        POE (81) castor oil                                         10      10        POE (25) hydrogenated castor oil                            10      10        POE (10) nonylphenol phosphate,                                               K salt                                                      ______________________________________                                    

(b) The compositions of part (a) are applied as a 20% emulsion, topolyester yarn (505 denier/34 filament) from a single merge so as toachieve 0.5-0.6% dry pick-up. The resulting texturized yarn has goodproperties.

EXAMPLE 19

Lubricants of the following compositions are prepared:

    ______________________________________                                        parts by weight                                                               A       B                                                                     ______________________________________                                        20.0    1.0       pentaerythritol tetralaurate                                39.3    58.3      trioctyl trimellitate                                       20.0    20.0      POE (9.5) nonylphenol laurate                               10.0    10.0      POE (10) nonylphenol                                        0.1     0.1       butylated hydroxytoluene                                    6.3     6.3       POE (9.5) nonylphenol phosphate                             2.5     2.5       triethanolamine (98%)                                       1.8     1.8       water                                                       ______________________________________                                    

EXAMPLE 20

Coning oil, for application at a level of 2-4% after texturizing, isprepared from:

    ______________________________________                                        parts by weight                                                               A       B                                                                     ______________________________________                                        7.50    1.0       pentaerythritol tetrapelargonate                            7.50    15.0      trioctyl trimellitate                                       3.75    3.75      POE (9.5) nonylphenol coconate                              10.00   10.0      POE (3.5) lauryl alcohol                                    2.50    2.50      POE (25) hydrogenated castor oil                            2.50    2.50      POE (10) nonylphenol phosphate                              64.15   64.15     Ucon LB-65                                                  0.10    0.10      butylated hydroxytoluene                                    1.00    1.00      triethanolamine                                             1.00    1.00      water                                                       ______________________________________                                    

The coning oil provides necessary lubrication to allow yarn to berapidly coned, knitted or woven.

EXAMPLE 21

An apparatus for removal of dye solutions of the invention consisted ofthree stainless steel columns, each 5 cm in diameter and 50 cm long.Each column was fitted with a circular pad (5 microns), in the center ofwhich was a hole 0.64 cm in diameter. The pad was covered with a disc ofstainless steel screen and topped with Whatman no. 1 filter paper.

The first column of the series was packed with 100-200 g of activatedgranular carbon (Calgon Corp.) and was used as a holding tank forheating the dye solution to about 185° C.

Each of the second and third columns was packed with about 500 g ofactivated carbon. The temperature of the liquid being passed throughthese columns was about 185° C. and 120° C., respectively.

Dye solutions (Disperse Blue 60 at a concentration of 5 g/l) in 80:20tris(2-ethylhexyl)trimellitate:bis(2-ethylhexyl)cycloaliphatic diesterby volume were decolorized in th foregoing series of three columns.About 15.5 liters of dye solution was decolorized by about 500 g ofactivated granular carbon. At a dye concentration of 5 g/liter, 1 poundof carbon will accordingly decolorize about 30 pounds of dye mixture.

Flow rates were varied from very slow to a rate of 1 gal/min/square footof surface area without adversely affecting recovery of the vehicles.

The foregoing apparatus was used for the decolorization of dyesolutions, containing 5-10 g/l of about 60 different dyes. The processneed not be carried out under an inert atmosphere.

EXAMPLE 22

Spin finish for polyamide is prepared from:

    ______________________________________                                        parts                                                                         ______________________________________                                        5           tris(2-ethylhexyl)trimellitate                                    5           pentaerythritol tetrapelargonate                                  5           POE (25) hydrogenated castor oil                                  5           POE (10) nonylphenol phosphate                                    80          water                                                             ______________________________________                                    

EXAMPLE 23

Dye solution is made from:

    ______________________________________                                        parts by weight                                                               ______________________________________                                        80           pentaerythritol tetrapelargonate                                 20           polyoxyethylene nonylphenol laurate                                           (9.5 moles of ethylene oxide)                                     1           Latyl Blue BCN 356                                               ______________________________________                                    

The dip dye solution is used as in Example 12, with similar results.

EXAMPLE 24

Forty grams of dye solution containing Disperse Blue in 80:20tris(2-ethylhexyl)trimellitate:pentaerythritol tetrapelargonate at alevel of 5 g of dye/liter are treated at 150° C. with 3 g of activatedcarbon. The hot solution is filtered through Whatman No. 1 filter paper.To the lightly-colored filtrate is added 1 g of activated carbon. Themixture is heated to 150° C. and filtered hot. The filtrate is lightyellow in color and can be used for a dye bath with another color dye.

EXAMPLE 25

Experiments similar to those of Example 24 are done with an 80:20 dyebath, containing 5-10 g/l of one of Disperse Red 60, Disperse Yellow 54,Nylanthrene Blue 2RFF (an acid dye) or Roma Violet Pigment RL 9613. Ineach case, treatment with about 10% by weight of activated carbon,referred to colorant weight, at 100°-200° C. results in essentiallyclean dye bath solution, which can be recycled without distillation.

EXAMPLE 26

Yarn lubricant was made from:

    ______________________________________                                        parts by weight                                                               A     B                                                                       ______________________________________                                        21    32      ethoxylated hydrogenated castor oil                                           (25 EO units)                                                    2     2      99.8% by weight of tris(2-ethylhexyl)trimellitate,                            0.2% by weight of 2,2'-oxamidobis[ethyl 3-(3,5-di-                            tert.-butyl-4-hydroxyphenyl)propionate]                          8     7      trimethylolpropane tripelargonate                                3    --      chlorowax                                                       66    59      triethyleneglycol dipelargonate                                 ______________________________________                                    

Each of the foregoing samples gave a friction measurement of 400 g onspun polyester. This compares very favorably with 300 g friction for acommercially available silicone lubricant.

EXAMPLE 27

Dye bath was prepared from triethyleneglycol dipelargonate, containing0.5% by weight of Disperse Blue 60. A polyester swatch, dipped into thebath at 185° C. for 1 min, gave a good level blue shade dyeing.

The preceding examples can be repeated with similar success bysubstituting the generically or specifically described reactants and/oroperating conditions of this invention for those used in the precedingexamples.

From the foregoing description, one skilled in the art can easilyascertain the essential characteristics of this invention and, withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various usages andconditions.

I claim:
 1. A waterless dip dye composition for apparel or otherarticles, made from plastic, comprising an aliphatic polyester of ahigher alkanoic acid and a polyol of the formula

    (ACOO).sub.2-6 B,

wherein A is alkyl of 8-22 carbon atoms and B is the residue of apolyhydric alcohol, other than glycerol, of 2-6 hydroxyl groups; andwhen B is the residue of glycerol, A is alkyl of 8, 10, 12, 14, 16, 18or 20 carbon atoms; and an organic colorant.
 2. The composition of claim1, further comprising at least 5% by weight of an aromatic polyester ofthe formula C₆ H_(z') (COOR₁)_(z), wherein R₁ is substituted orunsubstituted alkyl of 6-22 carbon atoms or the residue of analkylphenol ether of an alkoxyalkanol; z is 3, 4, 5, or 6 and z' is 6-zor of a cycloaliphatic diester of the formula ##STR5## wherein R issubstituted or unsubstituted straight or branched chain alkyl of 4-20carbon atoms, polyoxyalkylene of the formula R'(OC_(x) H_(2x))_(n) orphosphated polyoxyalkylene of the formula, (HO)₂ P(═O)(OC_(x)H_(2x))_(n) OC_(x) H_(2x) --, or a salt thereof, wherein (C_(x) H_(2x)O)_(n) is (C₂ H₄ O)_(n) --, (C₃ H₆ O)_(n) -- or (C₂ H₄ O)_(p) (C₃ H₆O)_(q) --; R' is H or ArCO; Ar is substituted or unsubstituted mono- orbicyclic aryl of up to 15 carbon atoms; x is 2 or 3; n is 2-22 and thesum of p+q is n.
 3. The composition of claim 2, containing at least 5%by weight of the aromatic polyester.
 4. The composition of claim 2,containing at least 5% by weight of a trialkyl trimellitate, whereinalkyl is of 6-22 carbon atoms.
 5. The composition of claim 2, containingat least 5% by weight of cycloaliphatic diester, wherein R is alkyl of6-20 carbon atoms.
 6. The composition of claim 1, which contains0.05-2.0% by weight of triphenyl phosphite.
 7. The composition of claim1, wherein the organic colorant is a disperse dye.
 8. The composition ofclaim 2, consisting essentially of trialkyl trimellitate, 15-90% byweight of pentaerythritol tetraalkanoate and organic colorant.
 9. Thecomposition of claim 8, wherein the trialkyl trimellitate istris(2-ethylhexyl)trimellitate and the pentaerythritol tetraalkanoate ispentaerythritol tetrapelargonate.
 10. The composition of claim 1,wherein the aliphatic polyester is triethyleneglycol dipelargonate. 11.A process for coloring articles, made from plastic, comprising exposingan article being treated to a composition of claim 1, maintained at atemperature from 100° C. to the temperature at which the plasticdegrades, for a time adequate to achieve the desired degree ofcoloration.
 12. The process of claim 11, wherein the plastic ispolyester, polyamide, polyurethane, an acrylonitrile ormethacrylonitrile polymer or copolymer, halogenated polyolefin or epoxy.13. The process of claim 11, wherein the article is immersed in thecoloring composition at a temperature of at least 140° C. for at least 1minute.
 14. The process of claim 11, wherein the article is sprayed withthe coloring composition and heated in a bath or oven to at least 140°C.
 15. The process of claim 11, including the further steps of cleaningthe colored article with a halogenated solvent and drying thethus-cleaned article.
 16. The process of claim 15, wherein thehalogenated solvent is perchloroethylene or trichloroethylene and thehalogenated solvent is collected and recycled to the process.
 17. Aprocess for coloring articles, made from polyester, polyamide,polyurethane, halogenated polyolefin, epoxy or acrylonitrile ormethacrylonitrile polymeric or copolymeric plastic, comprising exposingan article being treated to a waterless coloring composition of claim 8,maintained at 120°-235° C., for a time adequate to achieve the desireddegree of coloration.
 18. The process of claim 17, wherein the articleis immersed in the coloring composition at a temperature of at least140° C. for at least 1 minute.
 19. The process of claim 18, includingthe further steps of drying the colored article, cleaning the articlewith a halogenated solvent and drying the thuscleaned article.
 20. Aprocess for coloring articles, made from polyester, polyamide,polyurethane, halogenated polyolefin, epoxy or acrylonitrile ormethacrylonitrile polymeric or copolymeric plastic, comprising exposingan article being treated to a waterless coloring composition of claim 3,maintained at 120°-235° C. for a time adequate to achieve the desireddegree of coloration.
 21. A process for coloring articles, made frompolyester, polyamide, polyurethane, halogenated polyolefin, epoxy oracrylonitrile or methacrylonitrile polymeric or copolymeric plastic,comprising exposing an article being treated to a waterless coloringcomposition of claim 4, maintained at 120°-235° C. for a time adequateto achieve the desired degree of coloration.
 22. A process for coloringarticles, made from polyester, polyamide, polyurethane, halogenatedpolyolefin, epoxy or acrylonitrile or methacrylonitrile polymeric orcopolymeric plastic, comprising exposing an article being treated to awaterless coloring composition of claim 10, maintained at 120°-235° C.for a time adequate to achieve the desired degree of coloration.
 23. Awaterless dip dye composition of claim 1, further comprising at least 5%by weight of an additional optional dyeing assistant agent.
 24. Aprocess for coloring articles, made from plastic, comprising exposing anarticle being treated to a composition of claim 23, maintained at atemperature from 100° C. to the temperature at which the plasticdegrades, for a time adequate to achieve the desired degree ofcoloration.
 25. A textile-treating composition comprising at least 5% byweight of an aliphatic polyester of the formula (ACOO)₂₋₆ B, wherein Ais alkyl of 8-22 carbon atoms and B is the residue of a polyhydricalcohol, other than glycerol, of 2-6 hydroxyl groups; and at least 0.5%by weight of an emulsifier or optional dyeing assistant agent.
 26. Thecomposition of claim 25, wherein the emulsifier or optional dyeingassistant agent is selected from the group consisting of alkoxylatedalkylphenols and their esters, alkoxylated castor oil compounds,alkoxylated hydrogenated castor oil compounds, alkoxylated primaryalkanols, salts of phosphated alkoxylated primary alkanols or phenols ora mixture thereof.
 27. The composition of claim 25, further containingat least 0.5% by weight of a cycloaliphatic diester of the formula##STR6## wherein R is substituted or unsubstituted straight or branchedchain alkyl of 4-20 carbon atoms, polyoxyalkylene of the formulaR'(OC_(x) H_(2x))_(n) -- or phosphated polyoxy alkylene of the formula,(HO)₂ P(═O)(OC_(x) H_(2x))_(n) OC_(x) H_(2x) -- or a salt thereof,wherein (C_(x) H_(2x) O)_(n) -- is (C₂ H₄ O)_(n) --, (C₃ H₆ O)_(n) -- or(C₂ H₄ O)_(p) --(C₃ H₆ O)_(q) --; R' is H or ArCO; Ar is substituted orunsubstituted mono- or bicyclic aryl of up to 15 carbon atoms; x is 2 or3; n is 2-22 and the sum of p+q is n.
 28. The composition of claim 26,containing at least 5% by weight of one or more emulsifiers or optionaldyeing assistant agents.
 29. A textile-treating composition of claim 26,comprising a spin finish composition containing 1-40% by weight ofaliphatic polyester, 20-60% by weight of aromatic polyester and 10-50%by weight of one or more emulsifiers or optional dyeing assistantagents.
 30. The composition of claim 29, comprising 25-35% by weight ofaliphatic polyester and 25-35% by weight of aliphatic polyester.
 31. Atextile-treating composition of claim 26, comprising a lubricantcontaining 1-30% by weight of aromatic polyester, 30-90% by weight ofaliphatic polyester and 10-60% by weight of one or more optional dyeingassistant agents or emulsifiers.
 32. The composition of claim 31,comprising 50-75% by weight of aliphatic polyester and 1-15% by weightof aromatic polyester.
 33. The composition of claim 32, wherein thealiphatic polyester is a mixture of trimethylolpropane tripelargonateand triethyleneglycol dipelargonate.
 34. A textile-treating compositionof claim 26, comprising a coning oil containing 1-10% by weight ofaliphatic polyester, 5-20% by weight of aromatic polyester, 2-20% byweight of one or more emulsifiers or optional dyeing assistant agentsand 60-70% by weight of ethylene oxide-propylene oxide copolymer.
 35. Atextile-treating composition of claim 26, comprising a dyeing assistantagent for aqueous dye baths, containing 1-40% by weight of aliphaticpolyester, 20-90% by weight of aromatic polyester and 10-30% by weightof one or more optional dyeing assistant agents.
 36. The composition ofclaim 35, comprising 25-35% by weight of aliphatic polyester and 35-45%by weight of aromatic polyester.
 37. The composition of claim 35,comprising 40-60% by weight of aromatic polyester, plus optionalemulsifiers or dyeing assistant agents.